Chemical lighting device to store, initiate and display chemical light

ABSTRACT

A device for providing chemiluminescent light from a chemical reaction of suitable compounds in the presence of a fluorescent compound, the device being a self-contained light unit, the device comprising an outer flexible, cylindrical, light transmitting container for one reactive composition, and an inner, rigid container for another reactive composition. Flexing the outer container breaks the inner container, allowing the reactive compositions to mix and produce a reaction providing chemiluminescent light which is visible through the outer light transmitting container.

United States Patent Inventors Appl. No. Filed Patented AssigneeCHEMICAL LIGHTING DEVICE TO STORE, INITIA'I'E AND DISPLAY CHEMICAL LIGHTPrimary Examiner-Samuel S. Matthews Assistant Examiner--Kenneth C.Hutchison Attorney-Charles J Fickey ABSTRACT: A device for providingchemiluminescent light from a chemical reaction of suitable compounds inthe presence of a fluorescent compound, the device being a self- 6claimsfl6pmwing r 7 contained light unit, the device comprising an outerflexible, US. Cl 240/2.25, cylindrical, light transmitting container forone reactive com- 222/94, 222/541, 252/ 188.3 position, and an inner,rigid container for another reactive Int. Cl F2lk 2/00 composition.Flexing the outer container breaks the inner Field of Search 240/225;container, allowing the reactive compositions to mix and 102/378;161/196; 250/71; 222/(Inquired), 94, produce a reaction providingchemiluminescent light which is 136, 541 visible through the outer lighttransmitting container.

PATENTEU MAY 4 I97l 111111111 i 5 5 3 UW hM WWQH E E 1 Illlllll'lulll'lll Illl. Il!|||\ (WI /3 l I} l i A fIE. E

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INVENTORS HEl/VZ KURT WALTER VO/GIIT IgOYBERT LEE MYERS M QVM A T TORNEY CHEMICAL LIGHTING DEVICE TO STORE, INITIATE AND DISPLAY CHEMICAL LIGHTThis application is a continuation-in-part of our previous applicationSer. No. 674,296, filed Oct. I0, 1967, now abandoned.

This invention relates to systems and devices for providingchemiluminescent light incorporating chemical components which reactchemically and provide excitation for a fluorescent compound. Theinvention more particularly relates to systems and devices whereby thereactive components are maintained in a nonreactive condition untillight is desired, the systems incorporating means to bring saidcomponents into a reactive condition and means to display the resultantlight.

Under certain circumstances, it is desirable to have a source of visiblelight which is not electrically activated Light can be provided bychemical systems, wherein the luminosity is solely the result ofchemical reaction without provision of any electrical energy. Such lightis known as chemiluminescent light.

Chemiluminescent light may be useful where there is no source ofelectricity. For example, in emergencies where sources of electricalpower have failed, a chemiluminescent system could provide light. Sincethe system requires no exter nally generated source of energy, devicescan be made small and highly portable. Moreover, chemiluminescent lightis cold light and can be used where the heat of conventionalillumination is not desired. It is also useful where electrical meanscould cause a fire hazard, such as in the presence of flammable agents.Chemiluminescent light is also effective under water since there are noelectrical connections to short out. Thus it may be seen thatchemiluminescent light can have many useful applications.

A principal object of the present invention is to provide systems anddevices incorporating chemiluminescent components for the provision ofchemiluminescent light.

A further object of this invention is to provide means for containingchemically reactive chemiluminescent components in a nonreactivecondition and means to combine said components when desired to providechemiluminescent light.

A further object is to provide a self-contained, highly portablechemiluminescent lighting device having all chemical components thereinand in which the light is displayed.

Another object is to provide a chemiluminescent lighting device which isinexpensive to make, easy to activate and highly effective.

Another object of the invention is to provide an illuminated wand havinga chemiluminescent lighting system.

These and other objects of the invention will become apparent as thedescription thereof proceeds.

This invention comprises a device for the storage and subsequentadmixture and display of a multicomponent chemiluminescent system. Thedevice consists essentially of an elongated, transparent or translucentflexible outer tube and a ridged, breakable inner tube which runsparallel to the outer tube and which preferably is joined to the outertube, or relatively fixed at its ends with respect to the inner tube.The inner tube is filled (wholly or in part) with one component of atwocomponent chemical lighting system. The outer tube is filled with thesecond component. The outer tube is capped at both ends with a closurewhich may contain a recess which fits around the inner tube to hold itin place and which, if desired, may serve as a closure for at least oneend of the inner tube. Alternatively, the inner tube may be sealedseparately and attached to the outer tube at the ends or along thelongitudinal side in any convenient way.

To operate the device, the outer, flexible tube is bent causing theinner inflexible tube to fracture and thus mix the two components andinitiative light production. The outer translucent tube thus becomes alighted wand for display purposes.

It is clear that two or more inner tubes could be employed to storeseparately the components of a three or multiple-component chemicallighting system.

The chemiluminescent system of this invention thus comprises the deviceas described accommodating the admixture of at least twochemiluminescent components and providing for the admixture in thedevice of at least two chemiluminescent components comprising either (a)a component containing a chemiluminescent compound and a secondcomponent containing a hydroperoxide compound, either or both componentscontaining a diluent, or (b) a dry solid component containing both asolid chemiluminescent compound and a solid hydroperoxide compound and asecond component comprising a solvent for said solid chemiluminescentcompound and said solid hydroperoxide compound. Any other necessaryingredients for the production of chemiluminescent light, or forlifetime control, or for intensity improvement, or for storagestabilization must of course either be included in one of the two systemcomponents or included as additional components. In particular with thepreferred oxalic-type chemiluminescent compounds of this invention, afluorescent compound must be included in the system.

The preferred chemiluminescent light is obtained in this invention bythe reaction of a hydroperoxide with a chemiluminescent compositionwhich, in combination, comprises a chemiluminescent compound selectedfrom the group consisting of (I) an oxalic-type anhydride of the typedisclosed and claimed in the copending application, Ser. No. 485,920,which is hereby incorporated by reference, (2) an oxalic-type amide ofthe type disclosed and claimed in copending applications, Ser. Nos.520,052 and 547,782, which are hereby incorporated by reference, (3) anoxalic-type O-acyl-hydroxylamine of the type disclosed and claimed incopending application, Ser. No. 547,76], and (4) an oxalic-type esterdisclosed and claimed in application, Ser. No. 491,896, in the presenceof a fluorescer compound, and a solvent. Other suitable chemiluminescentcompounds are 3-arrtinophthalhydrazide, 3,4,S-triphenylimidazole,l0,lO'-dialkyl9,9'-biacridinium salts, and9-chlorocarbonyl-10-methylacridinium chloride. The latter is disclosedand claimed in copending application, Ser. No. 427,459. All of theforegoing provide chemiluminescence when reacted with a hydroperoxidecompound in the presence of a base. Other chemiluminescent materials aredescribed by K. D. Gunderman, Angew, Chemie, Int. Ed., 4, 566/l965.

The preferred chemiluminescent compound of this invention is anoxalic-type ester selected from the group consisting of (a) an ester ofan oxalic-type acid and an alcohol characterized by acid ionizationconstant in water greater than 1.3 X lOahl. and (b) a vinyl ester of anoxalic-type ester. Similarly, in a preferred embodiment thereof, thealcohol would be an aromatic alcohol substituted by a substituentcharacterized by a positive Hammett sigma value. The preferred speciesof oxalic-type esters include bis(substitutedphenyl)oxalate such asbis(2-nitrophenyl)oxalate, bis(2,4- dinitrophenyl)oxalate,bis(2,6-dichloro-4-nitrophenyl)oxalate,bis(3-trifluoromethyl-4'nitrophenyl)oxalate, bis(2-methyl-4,6-dinitrophenyl)oxalate, bis( l,2-dimethyl-4,6- dinitrophenyl)oxalate, bis( 2,4-dichlorophenyl )oxalate, bis(2,5-dinitrophenyl)oxalate, bis( 2-formyl-4-nitrophenyl)oxalate,bis(pentachlorophenyl)oxalate, bis( l,2-dihydro-2-oxol-pyridyl)glyoxal,bis-N-phthalmidyl oxalate. The preferred subspecies isbis(pentachlorophenyl)oxalate.

The peroxides employed in the components of this invention may be anyhydroperoxide compound. Typical hydroperoxides includet-butylhydroperoxide, peroxybenzoic acid, and hydrogen peroxide.Hydrogen peroxide is the preferred hydroperoxide and may be employed asa solution of hydrogen peroxide in a solvent or as an anhydrous hydrogenperoxide compound such as perhydrate of urea (urea peroxide), perhydrateof pyrophosphate (sodium pyrophosphate peroxide), perhydrate ofhistidine (histidine peroxide), sodium perborate, sodium peroxide, andthe like. Whenever hydrogen peroxide is contemplated to be employed, anysuitable compound may be substituted which will produce hydrogenperoxide.

The peroxide concentration may range from about 15 molar down to about10 molar, preferably about 2 molar down to about molar. The ester ofthis invention may be added as a solid or in admixture with a suitablesolid peroxide reactant or in a suitable diluent, or alternativelydissolved directly in a solution containing the peroxide reactant.

Typical dilucnts, which additionally may be used in conjunction with thenecessary diluent of this invention, are those .which do not readilyreact with a peroxide such as hydrogen peroxide, and which do not reactwith an ester of oxalic acid.

Where a solvent is employed with the hydroperoxide-containing componentof this invention said solvent can be any fluid which is unreactivetoward the hydroperoxide and which accommodates a solubility of at least0.01 M hydroperoxide. Typical solvents for the hydroperoxide componentinclude water; alcohols, such as ethanol or octanol; ethers, such asdiethyl ether, diamyl ether, tetrahydrofuran, dioxane,dibutyldiethyleneglycol, perfluoropropyl ether, and l,2-dimethoxyethane;and esters, such as ethyl acetate, ethyl benzoate, dimethyl phthalate,dioctylphthalate, propyl formate. Solvent combinations can, of course,be used such as concentrations of the above with aromatic anisole,tetralin, and polychlorobiphenyls, providing said solvent combinationaccommodates hydroperoxide solubility. However, when oxalictypechemiluminescent materials are used, strong electron donor solvents suchas dimethyl formamide, dimethyl sulfonide, and hexamethylphosphoramideshould not, in general, be used as a major solvent component.

Where a solvent is employed with a component containing thechemiluminescent material any fluid can be used providing said fluidsolubilizes at least 0.0l M concentration of the chemiluminescentmaterial and is unreactive toward the chemiluminescent material. Typicalsolvents include ethers, esters, aromatic hydrocarbons, chlorinatedaliphatic and aromatic hydrocarbons, such as those cited in thepreceding paragraph. For oxalic-type chemiluminescent compounds,hydroxylic solvents such as water or alcohols and basic solvents such aspyridine should not be employed since such solvents used in general,react with and destroy oxalic-type chemiluminescent compounds. Solventcombinations may, of course, be used but such combinations when usedwith oxalic-type chemiluminescent compounds should not include strongelectron donor solvents.

When a component comprising a solid chemiluminescent compound and asolid hydroperoxide is used, the solvent or solvent compositioncomprising the second component may vary broadly. Said solvent, however,should preferably dissolve at least 0.02 M concentrations of both, thehydroperoxide and the chemiluminescent compound, and for oxalic-typechemiluminescent compounds, strong electron donor solvents should beavoided as major solvent components.

The fluorescent compounds contemplated herein are numerous; and they maybe defined broadly as those which do not readily react on contact withthe peroxide employed in this invention, such as hydrogen peroxide;likewise, they do not readily react on contact with the chemiluminescentcompound.

A fluorescent compound is required for light emission when the preparedoxalic-type chemiluminescent compound of the invention is employed. Forother types of chemiluminescent compounds a fluorescer is not requiredbut may be used to shift the wavelength of emitted light toward the redregion of the spectrum so as to change the color of emitted light.Fluorescent compounds for use with oxalic-type chemiluminescentcompounds should be soluble in the reactive solvent at least to theextent of 0.0001 moles per liter.

Typical suitable fluorescent compounds for use in the present inventionare those which have a spectral emission falling between 330millimicrons and 1,000 millimicrons and which are at least partiallysoluble in any of the above dilucnts,

, if such diluent is employed. Among these are the conjugated polycyclicaromatic compounds having at least three fused rings, such asanthracene, substituted anthracene, benzanthracene, phenanthrene,substituted phenanthrene, naphthacene, substituted naphthacene,pentacene, substituted pentacene, and the like. Typical substituentsforall of these are phenyl, lower alkyl, chlorine, bromine, 'cyano, alkoxy(C,- -C and other like substituents which do not interfere with thelight-generating reaction contemplated herein.

Numerous other fluorescent compounds having the properties givenhereinabove are well known in the art. Many of these are fully describedin Fluorescence and Phosphorescence," by Peter Pringsheim, lntersciencePublishers, lnc., New York, NY. 1949. Other fluorescers are described inThe Color Index," Second Edition, Vol. 2, The American Association ofTextile Chemists and Colorists, 1956, pp. 2907-2923. While only typicalfluorescent compounds are listed hereinabove, the person skilled in theart is fully aware of the fact that this invention is not so restrictedand that numerous other fluorescent compounds having similar propertiesare contemplated for use herein.

A fluorescent oxalic-type ester, such as the oxalic acid ester of2-naphthol-3,6,8-trisulfonic acid, does not require a separatefluorescent compound to obtain light. Other typical fluorescent oxalicacid esters include esters of oxalic acid (I) 2-carboxyphenol, (2)2-carboxy-6-hydroxyphenol, (3) l,4- dihydroxy-9,lO-diphenylanthracene,and (4) 2-naphthol. Thus a reactant including a fluorescent oxalic-typeester would thereby include at least one fluorescent compound.

It has been found that the molar (moles per liter of diluent)concentrations of the major components of the novel composition hereindescribed may vary considerably. lt is only necessary that components bein sufiicient concentration to obtain chemiluminescence. The ester ofoxalic acid molar concentration normally is in the range of at leastabout l0 to 5 molar, preferably in the range of at least about 10' toabout 1 molar; the fluorescent compound is present in the range fromabout 10" to 5, preferably 10 to l0l molar; and the diluent must bepresent in a sufficient amount to form at least a partial solution ofthe reactants involved in the chemiluminescent reaction. If the ester isliquid, it may serve as'either the sole diluent or a partial diluent.

The wavelength of the light emitted by chemiluminescence of thecompositions of this invention, i.e., the color of the light emitted,may be varied by the addition of any one or more energy transfer agents(fluorescers) such as the known fluorescent compounds discussed atlength above.

The wavelength of the light emitted by the composition of this inventionwill vary, depending upon the particular fluorescent component employedin the reaction.

Additionally, it has been found that the superior intensity ofchemiluminescence is obtained when the final mixture producing theluminescence is maintained at a temperature of between about 40 C. and75 C., preferably between about 20 C. and 5 C. However, temperature isnot critical and the luminescence of Applicants process is not limitedto these ranges.

The lifetime and the intensity of the chemiluminescent light obtainedwith the preferred oxalic-type chemiluminescent compounds of thisinvention can be regulated by the use of certain regulators such as:

1. By the addition of base to the chemiluminescent composition. Both thestrength and the concentration of the base are critical for purposes ofregulation.

2. By the variation of hydroperoxide. Both the type and theconcentration of hydroperoxide are critical for the purposes ofregulation.

3. By the addition of water.

4. By the addition of a catalyst which changes the rate of reaction ofhydroperoxide with the oxalic-type ester. Catalysts which accomplishthat objective include those described in M. l... Bender, Chem. Revs,"Vol. 60, p. 53 (i960). Also, catalysts which alter the rate of reactionor the rate of chemiluminescence include those accelerators of copendingapplication, Ser. No. 577,595, and decelerators of copendingapplication, Ser. No. 577,615.

While acids are not in general accelerators for oxalic-typechemiluminescent reactions it should be noted specifically that acidsare accelerators for the oxalic amide chemiluminescent compounds ofcopending application, Ser. No. 547,782.

More specifically, the advantages obtained by the incorporation of acatalyst of Ser. No. 577,595 may be obtained in conjunction with theobjects of this present invention, by employing, according to thecopending application, an ionized salt having a cation selected from (a)an organic quaternary cation selected from the group consisting ofammonium, arsenic, and phosphorous, and (b) alkali metal having anatomic weight above 22, the salt of said cation preferably being solublein an organic solvent and preferably being characterized by a propertyof forming cation-aggregates when reacted with the oxalic-type ester anda hydroperoxide. One of the advantages is the fact that an excessiveamount of the chemiluyield may be obtained when the ionized salt isemployed, in contrast to systems not employing the accelerator wherebysuch systems would be limited to a much lower maximum concentration ofchemiluminescent agent which would continue to increase rather thandecrease the total quantum yield of chemiluminescent light.

Similarly, within the scope of the present invention is the concurrentemployment of one or more decelerators either alone in the compositionof this invention, or in conjunction with one or more of theaccelerators discussed in the preceding paragraphs. By employing one ofthe accelerators of the preceding paragraph, it would be possible toemploy a greater total concentration of the chemiluminescent agent whileconcurrently would be possible to employ a decelerator which wouldprolong the period during which the light of high intensity is obtainedfrom the chemiluminescent reaction. Such deoelerators set forth in thecopending application, Ser. No. 577,615, include for example a compoundsuch as oxalic acid.

When oxalate-type chemiluminescent compounds are used in a solutioncomponent it may be desirable to include a stabilizing agent such asthose described in copending application,Ser. No. 614,397.

The chemical compounds, components and their reactions for providingchemiluminescent light are described in copending, commonly assignedapplications, Ser. Nos. 442,802; 442,818, and those previouslymentioned, and as such they do not form a part of the present invention.

In this invention, the reactive components are stored in a multiplecompartment container device having a minimum of two compartments,wherein the separate components may be brought into contact to producethe reaction which provides chemiluminescent light to be displayed insaid container. When either the chemiluminescent compounds,hydroperoxide, or both are fluid, they must be in separate compartments.The diluent and fluorescent compounds can be in either of these twocompartments. If the chemiluminescent compounds, hydroperoxide andfluorescent compounds are dry powdered solids, they may be kept togetherin one compartment with the diluent in the other compartment. Thereactive components are brought together to provide chemilu minescentlight.

The invention may be better understood by reference to the drawings inwhich:

FIG. 1 shows one outer flexible tube for one embodiment of thechemiluminescent light device,

FIG. 2 shows the inner, rigid tube,

FIG. 3 shows one embodiment of an assembled device,

FIG. 4 shows the method of activation of the device.

Referring to FIGS. I and 2, the device comprises a flexible tube llpartly threaded at 2 to receive a threaded plug 3 to close opening 4 oftube 1. A second plug 5 is provided to close opening 6 at the oppositeend of tube 1 by a press fit. Both plugs 3 and 5 have a bore 7 forreceiving a tube 8 of a rigid, breakable material.

In FIG. 3, the assembled device is shown, with tube 8 fitted in plugs 3and 5, which are in turn fitted into openings 4 and 6 of tube 1, holdingtube 8 substantially parallel to the longituminescent agent maybeemployed'whereby a higher quantum dinal axis of tube 1 and relativelyfixed with respect to the ends of tube 1. Tube 8 is filled with onecomponent of the chemiluminescent system, previously described, forexample the chemiluminescent compound in a diluent.

Tube 1 is filled with the second component, described previously, suchas a hydrogen peroxide solution and a fluorescent compound.

Tube 1 is a flexible, transparent or translucent material, havingsufficient rigidity to maintain a shape, such as polyethylene,polypropylene, teflon and the like. Tube 7 is a rigid, breakable orfrangible material such as glass, or a relatively brittle thermosetresin, e.g., thin walled bakelite or other suitable material and neednot be transparent or translucent. Plugs 3 and 5 may be any suitablematerial such as plastic or wood. Plastics are particularly suitable inview of their ease of fabrication.

To activate the device and provide light, tube 1 is flexed '7 slightlyas shown in FIG. 4. Tube 7, which is rigid, has its ends fixed inparallel relation to plugs 3 and 5 in recesses 7 is bent and broken at anumber of points 9 allowing its contents to admix with that of tube 1 tobring about the chemiluminescent reaction and to obtain achemiluminescent light mixture within tube 1 and providechemiluminescent light emission visible through tube 1.

As shown in FIG. 5, the device may have more than one breakable tube 8,so that more than two chemiluminescent components may be kept separated.Such a system is useful where rate regulators such as acidic or basicmaterials may be used in the reaction.

The color of the light emission will depend on the type of fluorescentcompound and its spectral response. However, the visible color could bevaried by using a colored plastic for tube 1.

It will be obvious that the construction of the inventive device may bevaried so long as the basic requirements are maintained. For example,tube 8 could be open at one end and a recess 7 could be the means forclosing it. In addition, one end of tube 1 could be molded closed with arecess 7 as shown in FIG. 6. Moreover, tube 8 could be fitted withintube 1 in any suitable manner, so long as its ends are relative fixedwith respect to the ends of tube 1.

The invention provides a device for providing visible light whenever andwherever desired, independent of conventional electrical lightingmethods and without the hazards and limitations of electrical lighting.The chemiluminescent lighting systems can be especially useful inemergency situations where all other forms of lighting have failed. Thesystems do not have the fire of ignitable lighting devices such ascandles, gas, or oil lights.

It will be readily apparent that the chemiluminescent device is notconfined to emergency lighting, however. It can be used at any timewhere a cold, safe illuminating means is desired. It is also useful toprovide illumination where electrical illumination is unavailable. Thedevice is highly portable and can be hand held for signalling.

While certain specific embodiments and preferred modes of practice ofthe invention have been described, it will be understood that this issolely for illustration, and that various changes and modifications ofthe invention may be made without departing from the spirit of thedisclosure or the scope of the appended claims.

We claim:

1. A chemiluminescent light device comprising an outer flexible, lighttransmitting tube means and an inner rigid, breakable tube means,substantially coextensive with said outer tube means, a chemiluminescentcomponent in each said tube means, means to close said tube ends, andmeans to maintain said inner tube means relatively fixed with respect tosaid outer tube means.

2. The device of claim 1 comprising a pair of concentric tubes.

3. The device of claim 1 wherein said inner tube means comprises morethan one tube.

with recesses into which the ends of the inner tube means fit.

6. The device of claim 5 wherein said recesses comprise the closingmeans for the ends of the inner tube means.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,57 97 Dated May it, 1971 Inventm-(S) Heinz Kurt Walter Voight and Robert LeeMyers It is certified that error appears in the above-identified patentand that said Letters Patent are hereby corrected as shown below:

and insert 1.31:10'

Col. 2, line 75 delete "10 and insert 1O and insert 1O" Col. 2, line Ldelete "1.3Xl0ahl Col. 3, line 1 delete Col. 1;, line 31 delete "10 andinsert 10 Col. L line 32 delete "10 and insert 10" Col. LL, line 3hdelete "10 and insert 10" Col. 1;, line 314 delete "10 and insert 10Col. Ll, line BL; delete "1O '1" and insert 10" Col. LL, line 52 delete"C. and insert -20C.

Col. L4, line 52 delete "5C." and insert C.

Signed and sealed this 1 th day of January 1 972.

(SEAL) Attest: 1

EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Atte sting Officer ActingCommissioner of Patents

2. The device of claim 1 comprising a pair of concentric tubes.
 3. Thedevice of claim 1 wherein said inner tube means comprises more than onetube.
 4. The device of claim 1 wherein the means for closing the outertube means comprise plugs fitted to the ends thereof.
 5. The device ofclaim 4 wherein said plugs are provided with recesses into which theends of the inner tube means fit.
 6. The device of claim 5 wherein saidrecesses comprise the closing means for the ends of the inner tubemeans.